Diethylenetrimelamine and method



UNITED STATES PATENT omen.

DIETHYLENETRIMELAMINE AND METHOD OF PREPARING THE SAME James R. Dudley, Darien, Conn., assignor to American Cyanamid- Company, New York, N. Y., a corporation of Maine No Drawing. Application January 30, 1947, Serial No. 725,253

4 Claims. (01. 260--249.6) 1 2 This invention relates to a new chemical commatic, e. g., 4,alpha-tolylene, 3,beta-phenylenepound and to method of preparing the same, and ethyl, 4,alpha-xylylene, 2,gamma-phenylenebutmore particularly to the production of a new and yl, etc. Thus, R may represent a divalent hydrouseful triazine derivative, specifically diethylenecarbon radical represented by the formula trimelamine. 5 ArRAr where Ar represents an arylene The triazine derivatives of the general class radical and R" represents an alkylene radical.

with which this invention is concerned may be When n in Formula I represents 0 the chemical represented by the following general formula compounds of the general class with which this where R represents a member of the class coninvention is concerned may be represented by the sisting of hydrogen and monovalent hydrocarbon general formula radicals, R represents a divalent hydrocarbon H NH, NHB radical (that is, a divalent radical composed solely of carbon and hydrogen) bonded through carbon to nitrogen and containing not less than N N N N two carbon atoms, and n represents one of the il following: 0, a small whole number (e. g., 1, 2, 3, 4, 5, etc.), When n is 0 the triazine derivative N N co ta s O y tWO s-triazinyl Y where R and R have the same meanings as given nuclei. above with reference to Formula I.

Illustrative examples of monovalent hydrocar- Diethylenetrimelamine and other compounds bon radicals which R in the above formula may of the kind embraced by Formulas I and II may represent arei a iphatic (e. g., methyl, et y be used, for example, as flame-proofing agents, propyl, isopropyl, butyl, lsobutyl, sec.-buty1, fungicides or insecticides, or as components of butenyl, amyl, isoamyl, hexyl, octyl, decyl, dosuch materials, or in the preparation of derivadecyl, octadecyl, allyl, methallyl, crotyl, oleyl, tives thereof, e. g., ureido, methylol, methylene, linalyl, etc.), including cycloaliphatic (e. g., cyetc., derivatives of the individual compound emclopentyl, cyclopentenyl, cyclohexyl, cyclohexenbraced by Formula I. These compounds are yl, cycloheptyl, etc.) aryl (e. g., phenyl, biphenespecially valuable for use in the preparation of ylyl or xenyl, naphthyl, etc.) aliphatic-substisynthetic resinous compositions. Thus, they may tuted aryl (e. g., tolyl, xylyl, ethylphenyl, 2-bube condensed with, for instance, aldehydes, in-

tenylphenyl, tert.-butylphenyl, etc.); and aryleluding polymeric aldehydes, hydroxyaldehydes substituted aliphatic (e. g., benzyl, cinnamyl, and aldehyde-addition products, to yield resinphenylethyl, phenylpropyl, etc). Illustrative ous condensation products having particularexamples of divalent hydrocarbon radicalswhich utility in the plastics and coating arts. Such re- R in the above formula may represent are: diaction products are more fully described and are valent aliphatic, e. g., ethylene, propylene (trispecifically claimed in my copendingapplication methylene), propenylene, butylene, isobutylene, Serial No. 725,254 filed concurrently herewith, pentylene, isopentrylene, etc., including divalent now Patent No. 2,524,727, issued October 3, 1950.

cycloaliphatic, e. g., cyclopentylene, cyclopenten- More specific examples of chemical compounds ylene, cyclohexylene, cyclohexenylene, cycloembraced by Formulas I and II are the alkyleneheptylene, etc.; divalent aromatic, e. g., phenyldimelamines (e. g., ethylene dimelamine, the ene, naphthylene, etc.; divalent aliphatic-subpropylenedimelamines, the butylenedimelamines, stituted aromatic, e. g., 2,4-tolylene, ethyl-2,5- the pentylenedimelamines, hexamethylenedimelphenylene, isopropyl-3,4-phenylene, l-butyl-ZA- amine, decamethylenedimelamine, etc.); the arnaphthylene, etc.; divalent aromatic-substituted ylenedimelamines (e. g., the phenylenedimelaliphatic, e. g., phenylethylene, phenylpropylene, amines, the naphthylenedimelamines, the binaphthylisobutylene, xylylene, alpha-( l-tolylphenylenedimelamines, etc.); the aryl-substiene) beta-butyl, etc.; and radicals that may be tuted a kylenedimelamines (e. g., the phenylethclassed either as divalent aromatic-substituted ylenedimelamines, the phenylpropylenedimelaliphatic or divalent aliphatic-substituted aroamines, the naphthylisobutylenedimelamines, the

xylylenedimelamines, etc.) the alkylesubstituted arylenedimelamines ,(e. g., the tolylenedimelamines, the ethylphenylenedimelamines, the isopropylphenylenedimelamines, etc.); the dialkylene and diarylene trimelamines, the trialkylene and triarylene tetramelarnines, the tetralkylene and tetrarylene pentamelamines, the pentalky1- ene and pentarylene hexamelamines, the hexalkylene and hexarylene heptamelamines, etc., and the corresponding aromatic-substituted alkylene and aliphatic-substituted arylene polymelamines, examples of all of which will be apparent from the foregoing examples of the dimelamines and from the second and third paragraphs of this specification.

Various methods may be employed to produce the chemical compounds which are within the scope of Formulas I and II. Compounds represented by the general formula where R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and R. represents a divalent hydrocarbon radical bonded through carbon to nitrogen and containing not less than two carbon atoms, are prepared, for example, by effecting reaction under heat between (1) a triazine derivative represented by the general formula where X represents a halogen of the class consisting of chlorine and bromine, more particularly 2-chloro-4,6-diamino -1,3,5-triazine and 2- bromo-4,6-diamino-1,3,5-triazine, and (2) a diamine represented by the general formula V R 111 H-N-R -N-H where R and R have the meanings above given,

the reactants of (1) and (2) being employed in a molar ratio corresponding to approximately two mols of the triazine derivative of (1) per mol of the diamine of (2). Substantially more than two mols of the triazine derivative for each mol of the diamine may be used if desired. Compounds given, the reactants of (,1) and (2) being employed in a molar ratio corresponding -to approximately 2+n mols of the triazine derivative of (l) per mol of the polyamine of (2). If desired, substantially more than 2+n mols of the triazine derivative for each mol of the polyamine may be employed. In each case, that is, in producing the compounds represented by Formulas III and VI, the desired compound is then isolated from the resulting reaction mass.

Illustrative examples of polyamines (diamines, triamines, te'tramines, etc.) that may be employed, depending upon the particular end product desired, are listed below:

Ethylenediamine Diethylene triamine Triethylenetetramine Tetraethylenepentamine 1,2-butanediamine lA-butanediamine (tetramethylenediamine) 1,5-pentanediamine 0-, mand p-Phenylenediamines 1,2-propanediamine (1,2-diaminopropane) 1,3-prppanediamine (trimethylenecliamine) lA-naphthalenediamine lA-anthradiamine 3,3-biphenyldiamine 3,4-biphenyldiamine 4,4-diaminodiphenylmethane 1,2-bis- (cyclohexylamino) -ethane 1,2-bis- (phenylamino) -ethane 1,2-bis- (benzylamino) -ethane 1,2-bis- (methylamino) -ethane 1,2-bis-(to1ylamino) -ethane 1,2-bis-(allylamino) -ethane 1,3-bis- (nap-hthylamino) -propane 1,3 -bis- (xylylamino) -propane 1,4-bis- (phenylamino) -butane 1,4-bis- (phenylethylamino) -butane 1,5-bis- (cinnamylamino) -pentane 1,5-bis- (propylphenylamino) -pentane 1,3,5-triaminopentane 1,3,5-tris- (phenylamino) -pentane 1,3,5-tris- (Zbutenylamino) -pentane 1,3,5-tris- (decylamino) -pentane 1,3,5}?-tetraminoheptane 1,3,5,7-tetrakis- (tolylamino) -heptane 1,3,5,7,9-pentaminononane 1,3,5,7,9-pentakis- (ethylamino) -nonane 1,4-diamino-2-butene BA-diamino-l-butene 3,4-diamino-1-pentene lA-diamino-Z-pentene 5,6-diamino-1-hexene represented by the general formula Hexamethylenediamine NE; rim-( s (]J--NH9 NH, s Z N N o N Emi c- R- R') I I(R')-iN R-( J (LNHQ N L J where R and B have the same meanings as given Octamethylenediamine above with reference to Formula III and n represents a small whole number are prepared, for example, by effecting reaction under heat between (1) a triazine derivative of the kind represented by Formula IV and (2) a polyamine represented by the general formula H-N-(R' N) ,.1L'H

where R, R and n have the meanings heretofore Decamethylenediamine Octadecamethylenediamine The reaction between the chloro or bromo diamino triazine and the polyamine may be carried out in any suitable manner. Heat ordinarily is used at least to initiate the reaction. The reaction preferably is effected in the presence of a suitable solvent or mixture of solvents. Although various solvents and solvent mixtures may be employed, I prefer to use Water or a mixture of 1 added to the reaction mass after part of the poly amine has been caused to react with the chloro or bromine diamino triazine. In some cases, for example, in the preparation of alkylenepolymelamines, the function of the alkaline substances is to convert to the free base the polyamine hydro chloride or hydrobromide formed as a result of partial reaction between the'polyamine and the chloro or bromo triazine reactant. In other cases, for instance in the preparation of arylenepolymelamines, the function of the alkaline substance is to convert to the free base the arylenepolymelamine hydrochloride or hydrobromide that is formed by reaction between the polyamine and the chloro or bromo triazine reactant.

Illustrative examples of alkaline substances that may be employed as above described are the alkali-metal hydroxides and carbonates, more particularly the hydroxides and carbonates of sodium, potassium, lithium, caesium and rubidium; hydroxides of the alkaline-earth metals, e. g., barium hydroxide, calcium hydroxide, etc.; and magnesium hydroxide. The carbonates of alkali metals ordinarily are less desirable because of the greater difificulty in handling due to the carbon dioxide evolved. y

The reaction by which the compounds embraced by Formulas I and II are prepared is illustrated by the following equation with particular reference to the preparation of compounds of the kind embraced by Formula II under optimum conditions, that is, when a strongly alkaline substance, e. g., an inorganic base, is employed as heretofore described. In this equation the alkaline substance is shown for purpose of illustration as an alkali-metal hydroxide.

In this equation R, R and X have the same meanings as hereinbefore given and M represents an alkali metal.

As indicated hereinbefore, after partial reaction between the chloro or bromo diamino triazine and the diamine of Formula V or the polyamine of Formula VII, a strongly alkaline substance such, for instance, as an inorganic base (e. g., sodium hydroxide, potassium hydroxide and the other alkali-metal hydroxides) is preferably added to the reaction mass in an amount which is chemically equivalent to'the amount of said triazine derivative employed, and the reaction between the said reactants is then completed in the presence of the said base.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are dilute ammonia solution was slowly added 740 a parts of cyanuric chloride (approx. 4 mols) with moderate cooling to keep the temperature at I 40-45 C. The resulting slurry of 2-chloro-4,6-

mass just acid to phenolphthalein.

diamino-1,3,5-triazine was filtered off, and the filter cake was washed with water until free of ammonium chloride. I

The wet cake was slurried with 5000 parts of water and heated to reflux temperature. While heating the slurry, 178 parts of an approximately 67.5% aqueous solution of ethylenediamine (approx. 2.17 mols) was slowly added, keeping the solution neutral to phenol red. Thereafter 1600 parts of a 10% aqueous solution of sodium hydroxide was slowly added. The solution, which cleared after the addition of all of the sodium hydroxide solution, was refluxed for 2 hours and allowed to stand for about 16 hours, yielding a precipitate comprising ethylenedimelamine which was filtered ofi, washed with water, and dried at 105 C. The yield of the dried product amounted to 535 parts.

The impure material was dissolved in 2920 parts of warm 5% aqueous hydrochloric acid, filtered and reprecipitated by the addition of 1600 parts of 10% aqueous sodium hydroxide solution to the filtrate. The resulting precipitate was filtered off and washed with water until the acid solution thereof by means of a dilute aqueous I solution of sodium hydroxide as above described, washed each time until the washings showed the presence of no chloride ion, and then dried at 105 C. After this further purification the ethylenedimelamine, which has the structural formula melted at 314-316 C., and gave the following results upon analysis:

Percent N Calculated for CsHnNiz 60.41 Found 58.07

Example 2 Wet 2 chloro 4,6 diamino 1,3,5 triazine (2 mols) was slurried in 2000 parts of water and a small amount of phenolphthalein was added thereto. The slurry was heated to reflux while stirring and slowly adding an aqueous solution of ethylenediamine (1 mol), keeping the reaction The ethylenediamine could be added quite rapidly when and the mixture was refluxed for 1 hour after all of the caustic solution had been added. A precipitate comprising crude ethylenedimelamine v a product melting at 185-195 C.

by repeated reprecipitations from an aqueous hydrochloric acid solution with a dilute caustic soda solution.

Example 3 This example illustrates the preparation of diethylenetrimelamine, which has the structural formula Sixteen hundred and forty parts of an aqueous 28% ammonia solution was added to 6000 parts of water. To this solution was added slowly with stirring 110 parts of cyanuric chloride, and the reaction was allowed to proceed at 45 to 50 C. The resulting slurry was stirred for several hours and then was allowed to stand for about 16 hours. The precipitate comprising 2-chloro-4,6-diamino-l,3,5-triazine was filtered olT, and the filter cake was washed with water until free of ammonium chloride.

The wet cake was slurried with 7500 parts of water and thereafter slowly heated to refiux temperature. While heating to reflux, 206 parts of diethylenetriamine was slowly added to the slurry, while keeping the reaction mass acid to phenolphthalein. When all of the triamine had been added, 1600 parts of a 10% aqueous solution of sodium hydroxide was added slowly, yielding a strongly basic solution which was almost clear. Upon cooling the solution, crude diethylenetrimelamine was precipitated. The impure material was filtered olT, washed with water, and then was recrystallized from hot water. The yield of the purified product after drying at 105 C. was 96% of the theoretical. The diethylenetrimelamine was further purified by recrystallizing it two more times from hot water, yielding 4A-ditylenedimelamine, which has the struc- 6 tural formula parts of water and the resulting mixture was heated under reflux at the boiling temperature of the mass for 40 minutes, at the end of which period of time complete solution was obtained. A small amount of decolorizing carbon and 1000 parts of water were added, and heating was continued for 20 minutes. The reaction mass was filtered on a heated funnel. The solid comprising 4,4'-ditylenedimelamine hydrochloride, which separated on cooling, was extremely difiicult to filter. The hydrochloride was suspended in 4000 parts of water, and an aqueous solution of sodium hydroxide (2 mols) was added thereto. The resulting mixture was heated under reflux at the boiling temperature of the mass for 30 minutes, cooled and filtered to separate the ditylenedimelamine, which then was washed with water until the washings were neutral to pH paper. The dried, crude 4,4- ditylenedimelamine, which melted at 322-326 'C. with decomposition, amounted to 313 parts. This yield corresponds to about 75% of the theoretical.

A portion of the crude material was recrystallized twice as the hydrochloride from a dilute aqueous solution of hydrochloric acid and then converted to the free base by adding a dilute aqueous solution of sodium hydroxide. The purified product melted at 322-326 C. and gave the following results upon analysis:

Percent C (wet method) Calculated for C19H20N1Z 54.81 Found 55.68 55.74

Example 5 This example illustrates the preparation of 2- N,2-N-dicyclohexyl 2-N,2' N-ethy1enedimelamine, which has the structural formula The two first-named ingredients were suspended in 1500 parts of water and heated under reflux at boiling temperature until the reaction mass was neutral to pH paper. The above-stated amount of sodium hydroxide in the form of 0 a dilute aqueous solution was then added slowly to the refluxing mass, keeping the pH below 10 to XI N112 NH,

0 T H2NC\ //CNHC CHZC -HNC1I "-NH;

N v N phenolphthalein indicator. The total time of \pprox, heating under reflux was 5%; hours. The reac- Pms tion mass was filtered hot to separate crude 2- N ,2-N '-dicycloheXyl-2-N ,2 -N- ethylenedimel g chlo,.o 4,s diamino l,wmazm 29m 2 amine, and the filter cake was washed with wa- 4,4'-Diaminodiphenylmethanc 198.0 1 ter until the washings were neutral to pH paper.

After drying in an oven at 105 C. for

The above ingredients were added to 2000 5 hours, the yield of dried product, M. P. 275 C.

with deccrnpcsitlch, was 256 parts or 90.7% of the theoretical. The dried product was extracted with ethanol to remove any unreacted 1,2- bis- (cyclohexylamino) -ethane.

Forty parts of the dimelamine was dissolved 10 heated to refluii and an additional amount of alkali added thereto. The total amount of 20% aqueous NaOH solution added was 200 parts by volume. The decamethylenedimelamine which separated was filtered ofi, and the isolated matein 400 parts of a dilute aqueous solution of hydrorial was washed with water until the washings chloric acid, to which was added a small amount were neutral to pH paper. The washed material of decolorizing carbon. The mixture was rewas dried at 105 C., yielding a product which had fluxed for 1 hours and filtered hot. The hyamelting point of 168-1'78 C. drochloride of the dimelamine which separated A sample of decamethylenedimelamine which was converted to the free base by treatment with had been recrystallized as the hydrochloride a dilute sodium hydroxide solution. The prodfrom a dilute aqueous solution of hydrochloric uct comprising 2-N,2'-N-dicyclohexyl2-N,2'-N- acid and then converted to the free base with a ethylenedimelamine was filtered ofi, washed with dilute aqueous solution of sodium hydroxide was water until the washings were free of chloride recrystallized from aqueous ethyl alcohol. The ion, and then dried at 105 C. The dried proddried, purified material melted at 183195 C. uct melted at 325-328 C., followed by decomand gave the following results upon analysis: position at 330 C.

A sample of 2-N,2'-N-dicyclohexyl-2-N,2'-N'- %C %N ethylenedimelamine which was further purified by crystallization from an aqueous solution of Calculatedror CWHWN" ,2 43, ethylene glycol monoethyl ether melted at 335 Found 340 C. and gave the following results upon analysls: Per cent C Example 7 ggizg for C2H34N12 This example illustrates the preparation of 2- 55'31 N,2'-N'-diphenyl-2N,2-N- ethylenedimelamine,

mp 6 which has the structural formula This example illustrates the preparation of I N NH: decamethylenedimelamine, which has the structural formula XIII NH, NH: II I ll HrN-O yCNOHz-CH:NC /CNH2 N/ \N N/ \N v l Hs 5H5 HnN-E NH-- (CH1) m-HN-! g-NH; Approx. Parts Molar Ratio Approx. 40 Z-Chloro ifi-diamino-1,3,5-triazine 145.6 2 Parts Molar 1,2-Bls-(phenylammo)ethane 106.0 1

Ratio e The above ingredients were suspended in 1300 parts of water, and the mixture was heated under Sodium hydroxide 73 refiux at the boiling temperature of the mass for several hours. The resulting solution was fil- The chlorodiaminotriazine was suspended in tered. hot. The hydrochloride of 2-N,2-N'-di- 1750 parts of water, the decamethylenediamine ij ypg- ,2'; t which sepadded e and the resulting mixture w arated upon cooling the filtrate was filtered off. hea ed und r r flux at he b il mp r of The filtrate was made alkaline with a dilute soluthe m s r O e above-Stated tion of sodium hydroxide, and the solid 2-N,2-N'- amount of sodium hydroxide in the form of a 10% diphenyl-2-N,2'-N-ethylenedimelamine that sepaqueous Solution Was then added S OWly to the arated was removed by filtration. One hundred reflux ass a S a e that the D Of the and forty parts of the hydrochloride and 115 mass did not exc d 0- An Oil S p u parts of thefree base were obtained. The free on fu heating it solidified- One hour after base was converted to the hydrochloride and the the addition 0f th Sodium hydroXide Solution, two portions of hydrochloride were dissolved in the reaction mass was cooled and then filtered hot water, small amount of decolorizing carbon to Separate crude decamethylenedimelamineadded, and then filtered. The filtrate Was con- The filter cake was washed with Water un l the centrated to increase the yield of the hydrochlo- W shi s w n r o pH p p rf r d yride. The hydrochloride was converted to the mg in an Oven at C-, the yield of the crude free base asdescribed in previous examples. The product was 345 parts (theo etical, 3 D yield of dried, purified 2-N,2-N-diphenyl-2-N,2- I This product was soluble in hot butanol, dioxane N'-ethy1enedimelamine, M. P. 350-355 C., was

and ethylene glycol monoethyl ether but did not 209 parts or 77.5% of the theoretical. crystallize from these solvents. .A sample of the dimelamine which which had The a portion (300 Parts) Of the Crude been crystallized three times as the hydrochloride amethylehedimelamihe was dissolved in 1500 from a dilute aqueous solution of HCl and then P of Water i ing 154 parts (155 111015) converted to the free base by treatment with a of concentrated hydrochloric ac d- T e eo dilute, aqueous solution of NaOH melted at 350- methylenedimelamine hydrochloride which sep- 354 C. and gave the following results upon analarated on cooling was filtered ofi and then susysisz, pended in 1500 parts of water. To the cold aque Per cent C ous suspension was added a, 20% aqueous solugalculated for C20H22N12 55.80 tion of sodium hydroxide until the mass was 211- u Found" 55.31 kaline to phenolphthalein, after which it was 55.33

Examples of th r ompounds em raced b Formula I that may be produced as hereinbefore generally described are listed below:

Triethylenetetramelamine Tetraethylenepentamelamine Pentaethylenehexamelamine Hexaethyleneheptamelamine 1,3-cyclohexylenedimelamine 1,2-butylenedimelamine 1,4-buty1enedimelamine (tetramethylenedimelamine) 1,5-pentylenedimelamine mand p-Phenylenedimelamines 1,2-propylenedimelamine 1,3-propylenedime1amine 1,4-naphthylenedimelamine 1,4-anthrylenedimelamine 3,3-biphenylenedimelamine 3,4-biphenylenedime1amine Hexamethylenedimelamine Octamethylenedimelamine Octadecamethylenedimelamine 2 N,2 N dibutyl 2 N,2 N phenylenedimelamine 2 N,2 N dibenzyl 2 N,2 N ethylenedimelamine 2 N,2 N dimethyl 2 N,2 N ethylenedimelamine 2 N,2 N diisopropyl 2 N,2 N trimethylenedimelamine 2 N,2 N dinaphth-yl e 2 N,2 N a trimethylenedimelamine 2 N,2 N dicyclopentenyl 2 N,2 N trimethylenedimelamine 2 N,2' N dixylyl 2 N,2 N tetramethylenedimelamine 2 N,2 N diphenyl 2 N,2 N tetra.-

methylenedimelamine 2 N,2 N diphenylethyl 2 N,2 N tetramethylenedimelamine 2 N,2 N dicinnamyl 2 N,2' N tetramethyleoedimelamine 2 N,2 N diethyl 2 N,2' N pentamethylenedimelamine 2 N,2 N dipropylphenyl 2 N,2 N

pentamethylenedimelamine Butenylenedimelamines Pentenylenedimelamines Dibutenylenetrimelamines 2 N,2 N,2 N triallyl 2 N,2' N,2

N -diethylenetrimelamine 2 N,2' N,2 N tripropyl 2 N,2 N,

2 -N -diethylenetrimelamine 1,2,3 tris (2,4' diamino 1,3',5 triazinylamino) -propane 1,2,3 tris (N 2,4 diamino 1,3,5 triazinyl-N-phenylamino) -pr0pane 1,2,3 tris (N 2,4 diamino 1,3',5 triazinyl-N-pentylamino) -propane 1,3,5 tris (2,4 diamino 1,3,5 triazinylamino) -pentane 1,3,5,7 tetrakis (2,4 diamino 1,3,5 triazinylamino) -heptane 1,3,5,7 tetrakis (N 2,4 diamino 1,3',5

triazinyl-N-tolylamino) -heptane 1,3,5,7 tetrakis (N 2,4 diamino 1,3',5'

triazinyl-N-benzylamino) -heptane 1,3,5,7,9 pentakis (2,4 diamino 1,3,5'

triazinylamino) -nonane 1,3,5,7,9 pentakis (N 2,4 diamino 1,3,5-

triazinyl-N-cyclohexylamino) -n0nane 1,3,5,7,9 pentakis (N 2,4 diamino 1,3,5'-

triazinyl-N-decylamino) -nonane 12 Ot er exami es will b apparen to t o led the art fr m. t ex mp s o p m s af mentioned and from the second and third paragraphs of this specification.

' I claim:

1. Diethylenetrimelamine, the formula for which is 2. The method of preparing diethylenetrimelamine which comprises efiecting reaction under heat between 2-ch1oro-4,6-d iamino-1,3,5-triazine and diethylenetriamine in the ratio of approximately three mols of the former per mol of the latter, and isolating diethylenetrimelamine from the resulting reaction mass.

3. A method as in claim 2 wherein, after partial reaction between the 2-chloro-4,6-diamino- 1,3,5-triazine and the diethylenetriamine, an inorganic base in an amount which is chemically equivalent to the amount of said chlorodiaminotriazine employed is added to the reaction mass, and the reaction between the said reactants is completed in the presence of the said base.

4. The method of preparing diethylenetrimelamine which comprises forming an aqueous slurry of Wet, water-washed 2-chloro-4,6-diamino-1,3,5-triazine resulting from reaction in water between parts of cyanuric chloride and 1640 parts of aqueous 28% ammonia solution; heating the said aqueous slurry to reflux and during said heating slowly adding thereto 206 parts of diethylenetriamine while keeping the reaction mass acid to phenolphthalein indicator; adding slowly to the reaction mass, after all of the diethylenetriamine has been added, 1600 parts of a 10% aqueous solution of sodium hydroxide thereby to obtain a strongly basic solution; cooling the said basic solution whereupon diethylenetrimelamine precipitates; and separating the said diethylenetrimelamine from the said solution.

JAMES R. DUDLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,223,930 Griessback Dec. 3, 1940 2,294,873 DAlelio Sept. 1, 1942 2,295,574 Freidheim Sept. 15, 1942 2,306,439 Hentrich Dec. 29, 1942 2,333,493 DAlelio Jan. 4, 1944 2,368,451 DAlelio Jan. 30, 1945 2,392,607 Nagy Jan. 8, 1946 FOREIGN PATENTS Number Country Date 106,397 Switzerland 1924 106,401 Switzerland 1924 183,196 Switzerland 1936 OTHER REFERENCES Widmer: British Plastics, pp. 508-513, Feb. 1943.

Certificate of Correction Patent No. 2,544,071 March 6, 1951 JAMES R. DUDLEY It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 47, for isopentrylene read z'sopentylene; column 3, line 63, for the right-hand portion of the formula reading NR- read RN-; column 4, line 45, for (2butenylamin0) read (W-butmylamino) column 5, line 14, for substances read substance; column 7 line 25, for CH CH NH read UH 0H H1V-; column-9, line 13, for 2N,2N read 2-N,?-N; column 10, line 66, strike out the Word which, second occurrence; and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the casein the Patent Oflice.

Signed and sealed this 19th day of June, A. D. 1951.

THOMAS F. MURPHY,

Assistant flommissz'oner of Patents. 

1. DIETHYLENETRIMELAMINE, THE FORMULA FOR WHICH IS 